Chromatographic performance of monolithic and particulate stationary phases: Hydrodynamics and adsorption capacity

Monolithic chromatographic support structures offer, as compared to the conventional particulate materials, a unique combination of high bed permeability, optimized solute transport to and from the active surface sites and a high loading capacity by the introduction of hierarchical order in the interconnected pore network and the possibility to independently manipulate the contributing sets of pores. While basic principles governing flow resistance, axial dispersion and adsorption capacity are remaining identical, and a similarity to particulate systems can be well recognized on that basis, a direct comparison of sphere geometry with monolithic structures is less obvious due, not least, to the complex shape of the skeleton domain. We present here a simple, widely applicable, phenomenological approach for treating single-phase incompressible flow through structures having a continuous, rigid solid phase. It relies on the determination of equivalent particle (sphere) dimensions which characterize the corresponding behaviour in a particulate, i.e. discontinuous bed. Equivalence is then obtained by dimensionless scaling of macroscopic fluid dynamical behaviour, hydraulic permeability and hydrodynamic dispersion in both types of materials, without needing a direct geometrical translation of their constituent units. Differences in adsorption capacity between particulate and monolithic stationary phases show that the silica-based monoliths with a bimodal pore size distribution provide, due to the high total porosity of the material of more than 90%, comparable maximum loading capacities with respect to random-close packings of completely porous spheres.